Process of producing new dyestuffs of the anthraquinone series



"PROCESS OF PRODUCING NEW DYESTUFFS 01F THE ANTHRAQUINONJE SERIES lPaul Nawiasky and Rudolf Robl, Ludwigsllafenon-tlhe-Rhine, Germany, assignors to General Aniline Works, lino, New York, N. iii, a corporation of Delaware No Drawing. Application October 23,1934, Serial No. 749, 71. In Germany November 1, 1933 9 Claims. (401. '26059) The present invention relates to newdyestufis sample withdrawn and worked updissolves in of the anthraquinone series and a process of proa mixture of benzoyl chloride and trichlorbenducing same. zene (1:5) giving a blue-violet solution and the We have found that new dyestuffs of the ansolution in a. mixture of benzoyl chloride and para-diaminochrysazine, which has the formula: the characteristic absorption bands of the'initial material in the'same solvent mixture have 011 0H almost or entirely disappeared. This is usually the case after heating for about 4 hours. The

precipitate filtered oil by suction, washed-and worked up into a dyestufi paste in the usual H manner.

NH2 0 NEH The resulting dyestuff which is "most probably under such conditions as regards the period of chrysazine and para di(monomethylamno) the concentration of the reagents and chrysazine dissolves in concentrated sulfuric acid the temperature that the amino groups are only giving a yellow coloration which after the adpartiauy alkylated- The period of reaction is dition of boric acid turns ruby without a flu- 20 generally between about one hour and about five hours. The best reaction-temperature is between about 100 and 160 C. The end of the reaction can readily be ascertained by working Emm le 2 up a sample of the reaction mixture and dissolvclear blue shades .of great color strength.

zene (1:5). The reaction is finished when two at from With 50 p s of onovof the bands present in the absorption spectrum methyl Sulfate until a Sample W hd awn and of the starting material have almost or just en- Worked p s h p p s des r bed in EX- tirely disappeared. The solution of the new dyeample The Solution is then po d into ceacid is greenish-blue whereas the solution of the tered off by suction and washed with water until starting materials therein is violet. neutral.

Suitable alkylating agents .are for example Example 3 monoand di-alkyl esters of sulfuric acid, arylalkylene oxides. Instead of the monomethyles- Zine 100 parts of orthmdichlorbenzenel 1 ter of sulfuric acid a mixture of methanol and of Potash and 4 parts of dlmethyl'sulfate ulfuri acid may be employed ed to boiling whilestirring under reflux until a The new dyestuffs-which are obtained in good Sample withdrawn and Worked up has the propesters and ethers and may also be employed as non o the excess Potassium h t th intermediate products for the preparation of ortho-dichlorbenzene is expelled by distillation other dyestuffs with steam and the dyestuif is'filtered ofiby suc- The following examples will furth illustrate tion, washed until neutral and worked up into a how the said invention may be carried out in pasteipractice but the invention is not restricted to Eiwmple 4 these examples. The parts are by weight.

A mixture of l0'parts of para-diaminochrysaple 1 zine, 100 parts of ortho-dichlorbenzene, parts 50 750 parts of methanol are gradually added of p-ota'ssium carbnat? and parlfs P diethyl whilefstirring to a solution of 500 parts of para- Sulfate lsheated o lmg Whlle stirring und diaminochrysazine in 2000 parts of 96 per cent reflux 1mm a semple Wlthdrawn Worked p sulfuric acid, the temperature preferably being reacts in a simllar #181111?r as e bed 1n EX- kept below 60 C. The reaction mixture is then ample The Teaclllon mlXturB S then Worked 55 heated, for example up to about 140 0., until a up as described in Example 3.

thraquinone series can be obtained by alkylating benzene (1:5) gives aspectrum in which two of l reaction mixture is then poured onto ice, the

a mixture of para-amino-monomethylamino-' orescence effect. It dyes acetate artificial silk ing it in a mixtureof benzoyl chloride and ben- 5 parts of para-d am n rysazin a e heated.

stuffs in a mixture of acetic anhydride and boric C Water a d h precipitated y fi 's sulfonic acid esters, hydroxyalkyl halides and A mixture of 10 parts of pam'diammochrysa" 40 yields are especially suitable for dyeing cellulose ewes described in Example After neutraliza' Ermmple 5 5 parts of para-diaminochrysazine are heated to boiling in a vessel provided with a stirrer and a reflux condenser with 100 parts of trichlorbenzone, 5 parts of soda and 5 parts of toluene sulfonic acid butyl ester until a sample withdrawn and worked up reacts in a similar manner as described in Example 1. The trichlorbenzene employed is then removed by distillation with steam and the reaction product worked up in the usual manner.

Example 6 parts of para-diaminochrysazine are heated to boiling in a suitable vessel with 50 parts of ethylene chlorhydrin and 3 parts of sodium acetate until a sample withdrawn and worked up reacts in a similar manner as described in Example 1. The reaction mixture is then poured into water and the precipitated dyestufi is filtered 01f by suction, washed and worked up into a dyestuff paste.

Erample 7 A mixture of 20 parts of para-diaminochrysazine, 400 parts of ortho-dichlorbenzene, 10 parts of ethylene oxide and 0.5 part of sodium acetate ture, as for example is heated in an autoclave at elevated temperafrom 120 to 150 C., until a sample withdrawn and worked up reacts in a similar manner as described in Example 1. After removing the ortho-dichlorbenzene by steam distillation, the reaction mixture is worked up in the usual manner.

Example 8 w the anthraquinone series which comprises alkylating para-diaminochrysazine under such conditions as regards the period of reaction, the concentration of the reagents and the temperature that the amino groups are only partially alkylated, the end of the reaction being ascertained by the fact that a solution of a sample withdrawn, worked up and dissolved in a mixture of benzoyl chloride and benzene (1:5) gives a spectrum in which two of the characteristic absorption bands of the initial material have almost or just entirely disappeared.

2. The process of producing new dyestuffs of the anthraquinone series which comprises alkylating para-diaminochrysazine with a com- 1 pound selected from the group consisting of mono and di-alkyl esters of sulfuric acid, arylsulfonic acid esters, hydroxy alkyl halides and alkylene oxides under such conditions as regards the period of reaction, the concentration of the reagents and the temperature that the amino groups are only partially alkylated, the end of the reaction being ascertained by the fact that a solution of a sample withdrawn,

worked up and dissolved in a mixture of benzoyl chloride and benzene (1:5) gives a spectrum in which two of the characteristic absorption bands of the initial material have almost or just entirely disappeared.

3. The process of producing new dyestuffs of the anthraquinone series which comprises methylating para-diaminochrysazine with a compound corresponding to the formula wherein one B stands for --O.CH3 and the other R for -OH, -O.CH3 or aryl, the end of the reaction being ascertained by the fact that a solution of a sample withdrawn, worked up and dissolved in a mixture of benzoyl chloride and benzene (1:5) gives a spectrum in which two of the characteristic absorption bands of the initial material have almost or just entirely disappeared. l. The dyestuffs of the anthraquinone series corresponding to the general formula:

it Al l wherein one A stands for an amino group and the other A for an amino group which may contain up to two alkyl groups.

5. The mixture of para-amino-monomethylamino-chrysazine and para-di(monomcthylamino) -chrysazine.

6. The dyestuffs of the anthraquinone series which are substantially identical with the dyestuffs obtainable according to claim 1.

'7. The dyestuffs of the anthraquinone series substantially identical with the dyestufi obtainable by treating para-diaminochrysazine with a mixture of methanol and concentrated sulfuric acid at about 140 C. until a sample worked up and dissolved in a mixture of benzoyl chloride and benzene (1:5) gives a spectrum in which two of the characteristic absorption bands of the initial material in the said solvent mixture have just entirely disappeared.

8. The dyestuifs of the anthraquinone series which are substantially identical with the dyestuif obtainable by boiling para-diaminochrysazine with diethyl sulfate in the presence of a halogen-containing aromatic hydrocarbon until a sample worked up and dissolved in a mixture of benzoyl chloride and benzene (1:5) gives a spectrum in which two of the characteristic absorption bands of the initial material in the said solvent mixture have just entirely disappeared.

9; The dyestuffs of the anthraquincne series which are substantially identical with the dyestuif obtainable by boiling para-diaminochrysazine with ethylene chlorhydrin and a little sodium acetate until a sample worked up and dissolved in a mixture of benzoyl chloride and benzene (1:5) gives a spectrum in which two of the characteristic absorption bands of the initial material in the said solvent mixture have just entirely disappeared.

PAUL NAWIASKY. RUDOLF ROBL. 

